EP3409648B1 - Vitrocéramique à base de silicate de lithium ayant une phase cristalline powellite ou scheelite - Google Patents

Vitrocéramique à base de silicate de lithium ayant une phase cristalline powellite ou scheelite Download PDF

Info

Publication number
EP3409648B1
EP3409648B1 EP17174068.1A EP17174068A EP3409648B1 EP 3409648 B1 EP3409648 B1 EP 3409648B1 EP 17174068 A EP17174068 A EP 17174068A EP 3409648 B1 EP3409648 B1 EP 3409648B1
Authority
EP
European Patent Office
Prior art keywords
glass ceramic
glass
ceramic according
scheelite
powellite
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP17174068.1A
Other languages
German (de)
English (en)
Other versions
EP3409648A1 (fr
Inventor
Marc Dittmer
Christian Ritzberger
Markus Rampf
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ivoclar Vivadent AG
Original Assignee
Ivoclar Vivadent AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ivoclar Vivadent AG filed Critical Ivoclar Vivadent AG
Priority to ES17174068T priority Critical patent/ES2862162T3/es
Priority to EP17174068.1A priority patent/EP3409648B1/fr
Priority to US15/989,856 priority patent/US10626045B2/en
Publication of EP3409648A1 publication Critical patent/EP3409648A1/fr
Application granted granted Critical
Publication of EP3409648B1 publication Critical patent/EP3409648B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • C03C10/0009—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing silica as main constituent
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/831—Preparations for artificial teeth, for filling teeth or for capping teeth comprising non-metallic elements or compounds thereof, e.g. carbon
    • A61K6/833—Glass-ceramic composites
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • C03C10/0018—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents
    • C03C10/0027—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents containing SiO2, Al2O3, Li2O as main constituents
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • C03C10/0036—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and a divalent metal oxide as main constituents
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • C03C4/0007—Compositions for glass with special properties for biologically-compatible glass
    • C03C4/0021—Compositions for glass with special properties for biologically-compatible glass for dental use
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2204/00—Glasses, glazes or enamels with special properties

Definitions

  • the invention relates to lithium silicate glass ceramic with scheelite and / or powellite as a further crystal phase, which is particularly suitable for use as a dental material, preferably for the production of dental restorations, and precursors for the production of this glass ceramic.
  • Lithium silicate glass ceramics are characterized by very good mechanical properties, which is why they have been used for a long time in the dental sector and there primarily for the production of dental crowns and small bridges.
  • the known lithium silicate glass ceramics usually contain SiO 2 , Li 2 O, Al 2 O 3 , alkali metal oxides such as Na 2 O or K 2 O and nucleating agents such as P 2 O 5 as main components.
  • they can be used as additional components, for example, other alkali metal oxides, Contain alkaline earth metal oxides and ZnO as well as coloring and fluorescent metal oxides in small amounts.
  • DE 24 51 121 describes lithium disilicate glass ceramics that contain K 2 O and Al 2 O 3 and P 2 O 5 . They are made from corresponding germ-containing starting glasses, which are heated to temperatures of 850 to 870 ° C to crystallize lithium disilicate.
  • EP 2 377 830 A1 describes lithium silicate dental glass ceramic containing 9.0 to 30.0% by weight of transition metal oxide selected from the group consisting of oxides of yttrium, oxides of transition metals with atomic number 41 to 79 and mixtures of these oxides. This is characterized by a high refractive index with very good mechanical and optical properties.
  • the dental glass ceramic contains KAlSiO 4 and LaPO 4 as further crystal phases. Colorants and / or fluorescent agents, for example CeO 2 , Er 2 O 3 or Tb 4 O 7 , can also be present.
  • WO 2013/053868 A2 relates to lithium silicate glass-ceramic which contains hexavalent metal oxide selected from MoO 3 , WO 3 and mixtures thereof in an amount of 0.1 to 8.4% by weight and is suitable for use in dentistry.
  • lithium silicate lithium orthophosphate and quartz can be present as further crystalline phases in the glass ceramic.
  • EP 3 150 563 A1 and WO 2015/173394 A1 describe glass ceramics that contain lithium silicate and calcium scheelite.
  • the invention is therefore based on the object of providing a lithium silicate glass ceramic which can be used as a dental material and, if necessary, can be distinguished particularly easily from the natural tooth material surrounding it.
  • the glass ceramic should be suitable for use as a restorative dental material with advantageous mechanical and optical properties and for simple processing into dental restorations.
  • the invention also relates to the starting glass with germs according to claim 17, the method for producing the glass ceramic according to claims 18 and 19 and the use of the glass ceramic and the starting glass with germs according to claim 20.
  • the lithium silicate glass ceramic according to the invention is characterized in that it contains 0 to 6.0% by weight CaO and lithium silicate as the main crystal phase and scheelite in the form of Ca-scheelite (CaWO 4 ) and / or Sr-scheelite (SrWO 4 ) and / or Powellite in the form of Ca-Powellite (CaMoO 4 ) and / or Sr-Powellite (SrMoO 4 ) as further crystal phases.
  • the glass ceramic therefore contains scheelite, powellite or a mixture of these as further crystal phase (s).
  • the lithium silicate glass ceramic according to the invention fluoresces when excited with UV light with a wavelength of 254 nm.
  • the fluorescence properties are achieved here by the scheelite and / or powellite crystals contained, with scheelite showing a blue-white fluorescence and powellite a green-yellow fluorescence.
  • This fluorescence can be used advantageously, for example, to make dental restorations made of the lithium silicate glass ceramic according to the invention clearly distinguishable from natural tooth material.
  • the lithium silicate glass ceramic according to the invention is achieved by the double controlled crystallization of the crystal phases of lithium silicate on the one hand and on the other hand scheelite and / or powellite can be formed.
  • the crystal phases mentioned can be generated from corresponding starting glasses by targeted nucleation and crystallization. The nucleation and growth of both crystal phases in a homogeneous, non-phase-separated starting glass apparently take place as parallel solid-state reactions.
  • the glass ceramic has a combination of desirable optical and mechanical properties as well as processing properties which are advantageous for use as a dental material.
  • it is characterized by high strength, high X-ray opacity and fluorescence when excited with far-away UV light.
  • Many secondary crystal phases have a negative effect on the optical properties of lithium silicate glass ceramics. For example, they can reduce the translucency and they can also impair the colorability of the glass-ceramic, which can lead to considerable difficulties when imitating the color of the natural tooth material to be replaced.
  • the lithium silicate glass ceramic according to the invention preferably contains 51.0 to 77.0, in particular 55.0 to 75.0 and preferably 64.0 to 74.0% by weight of SiO 2 .
  • the lithium silicate glass ceramic contains 8.0 to 20.0, in particular 11.0 to 17.0 and particularly preferably 13.0 to 15.0% by weight of Li 2 O.
  • a lithium silicate glass-ceramic is preferred in which the combined amount of CaO and SrO 0.1 to 10.0, preferably 0.5 to 7.0 and particularly preferably 1.0 to 5.0% by weight.
  • a lithium silicate glass ceramic which contains 0.1 to 4.0 and particularly preferably 0.5 to 2.0% by weight of CaO is also preferred.
  • the lithium silicate glass ceramic according to the invention contains 0 to 10.0, in particular 0.1 to 7.0 and preferably 0.5 to 4.0% by weight of SrO.
  • a lithium silicate glass ceramic is also preferred which contains 0 to 12.0, in particular 1.0 to 8.0 and preferably 3.0 to 5.0% by weight of MoO 3 .
  • the lithium silicate glass ceramic contains 0 to 22.0, in particular 1.0 to 14.0 and preferably 4.0 to 7.0% by weight of WO 3 .
  • a lithium silicate glass ceramic according to the invention which contains 1.5 to 6.0, in particular 2.0 to 5.0 and preferably 2.5 to 4.5% by weight of P 2 O 5 . It is believed that P 2 O 5 acts as a nucleating agent.
  • the lithium silicate glass ceramic in addition to Li 2 O, further alkali metal oxide Me I 2 O in an amount of 0 to 6.0, in particular 1.0 to 5.0 and particularly preferably 1.5 to 4.0 wt. -% contains.
  • the term "further alkali metal oxide Me I 2 O” denotes alkali metal oxide with the exception of Li 2 O, this further oxide Me I 2 O being selected in particular from Na 2 O and K 2 O.
  • the lithium silicate glass ceramic particularly preferably contains at least one and in particular all of the following other alkali metal oxides Me I 2 O in the specified amounts: component Wt% Na 2 O 0-6.0, especially 0.1-6.0 K 2 O 0-4.5, in particular 0.1 to 4.5
  • the lithium silicate glass ceramic contains, in addition to CaO and SrO, further oxide of divalent elements Me II O in an amount of 0 to 4.0 and in particular 1.0 to 3.5% by weight, this further oxide Me II O is selected in particular from MgO and ZnO.
  • the lithium silicate glass ceramic particularly preferably contains at least one and in particular all of the following further oxides of divalent elements Me II O in the specified amounts: component Wt% MgO 0-4.0, especially 0.1-4.0 ZnO 0-4.0, especially 0.1-4.0
  • a lithium silicate glass ceramic according to the invention is also preferred which contains 0 to 11.0 and in particular 1.0 to 9.0 wt.% Oxide of trivalent elements Me III 2 O 3 , this oxide Me III 2 O 3 being selected in particular of Al 2 O 3 , B 2 O 3 , Y 2 O 3 , La 2 O 3 and Er 2 O 3 .
  • the lithium silicate glass ceramic particularly preferably contains at least one and in particular all of the following oxides of trivalent elements Me III 2 O 3 in the specified amounts: component Wt% Al 2 O 3 0-11.0, in particular 0.1 to 11.0, preferably 1.0 to 5.0 B 2 O 3 0-7.0, especially 0.1 to 7.0 Y 2 O 3 0-10.0, especially 0.1-10.0 La 2 O 3 0-3.0, especially 0.1-3.0 He 2 O 3 0-3.5, especially 0.1 to 3.5
  • a lithium silicate glass ceramic which contains further oxide of tetravalent elements Me IV O 2 in an amount of 0 to 11.0% by weight.
  • further oxide of tetravalent elements Me IV O 2 denotes tetravalent oxides with the exception of SiO 2 , this further oxide Me IV O 2 being selected in particular from ZrO 2 , GeO 2 , MnO 2 and SnO 2 .
  • the lithium silicate glass ceramic particularly preferably contains at least one and in particular all of the following further oxides of tetravalent elements Me IV O 2 in the specified amounts: component Wt% ZrO 2 0-11.0, especially 0.1-11.0 GeO 2 0-9.5, especially 0.1 to 9.5 SnO 2 0-7.0, especially 0.1 to 7.0 MnO 2 0-2.5, especially 0.1 to 2.5
  • a lithium silicate glass ceramic which contains further oxide of pentavalent elements Me V 2 O 5 in an amount of 0 to 11.5 and in particular 1.0 to 5.0% by weight.
  • the term "further oxide of pentavalent elements Me V 2 O 5" denotes pentavalent oxides with the exception of P 2 O 5 , this further oxide Me V 2 O 5 being selected in particular from V 2 O 5 , Ta 2 O 5 and Nb 2 O 5 .
  • the lithium silicate glass ceramic particularly preferably contains at least one and in particular all of the following further oxides of pentavalent elements Me V 2 O 5 in the specified amounts: component Wt% V 2 O 5 0-2.5, especially 0.1 to 2.5 Ta 2 O 5 0-2.0, especially 0.1-2.0 Nb 2 O 5 0-11.5, especially 0.1 to 11.5
  • a lithium silicate glass ceramic according to the invention which contains 0 to 2.0 and in particular 0.1 to 1.0% by weight of fluorine.
  • a lithium silicate glass ceramic according to the invention is particularly preferred which, independently of one another, contains at least one and preferably all of the following components in the specified amounts: component Wt% SiO 2 51.0-77.0 Li 2 O 8.0-20.0 SrO 0-10.0 MoO 3 0 - 12.0 WHERE 3 0-22.0 Me I 2 O 0 - 6.0 Me II O 0-4.0 Me III 2 O 3 0-11.0 Me IV O 2 0-11.0 P 2 O 5 1.5-6.0 Me V 2 O 5 0-11.5 fluorine 0 - 2.0 where Me I 2 O, Me II O, Me III 2 O 3 , Me IV O 2 and Me V 2 O 5 have the meaning given above.
  • the properties of the lithium silicate glass ceramic are significantly influenced by the crystal phases.
  • the glass ceramic according to the invention contains lithium silicate as the main crystal phase.
  • the term “lithium silicate” denotes at least one crystal phase selected from lithium disilicate and lithium metasilicate.
  • the glass ceramic according to the invention therefore contains lithium disilicate, Lithium metasilicate or a mixture of lithium disilicate and lithium metasilicate as the main crystal phase.
  • the glass ceramic according to the invention contains lithium disilicate as the main crystal phase.
  • main crystal phase denotes the crystal phase which has the highest mass fraction of all the crystal phases present in the glass ceramic.
  • the masses of the crystal phases are determined in particular using the Rietveld method.
  • a suitable method for the quantitative analysis of the crystal phases using the Rietveld method is, for example, in the dissertation by M. Dittmer "Glasses and glass ceramics in the MgO-Al2O3-SiO2 system with ZrO2 as nucleating agent", University of Jena 2011 described.
  • the glass ceramic according to the invention also contains scheelite and / or powellite as further crystal phases.
  • Scheelite is in the form of Ca-Scheelite (CaWO 4 ) and / or Sr-Scheelite (SrWO 4 ) and powellite in the form of Ca-Powellite (CaMoO 4 ) and / or Sr-Powellite (SrMoO 4 ).
  • the glass ceramic according to the invention can also contain further crystal phases, such as, for example, Li 3 PO 4 and / or SiO 2 modifications.
  • the type and the amount of crystal phases formed can be controlled in particular by the composition of the starting glass and the method for producing the glass ceramic.
  • the examples illustrate this on the basis of the variation in the composition and the production process.
  • the scheelite and powellite crystal phases contained in the lithium silicate glass ceramic are also X-ray opaque due to their composition. This leads to an advantageous contrast between natural and artificial material on x-rays, as used in particular in the dental field.
  • the lithium silicate glass ceramic according to the invention has a radiopacity according to EN ISO 4049 of in particular more than 120%, preferably more than 150% and particularly preferably more than 180%.
  • the lithium silicate glass ceramic according to the invention also has a biaxial breaking strength ⁇ Biax of preferably at least 300 MPa, in particular more than 350 and preferably more than 400 MPa.
  • the biaxial breaking strength was determined according to ISO 6872 (2015) (piston-on-three-ball test).
  • the lithium silicate glass ceramic has a thermal expansion coefficient CTE according to ISO 6872 (2015) (measured in the range from 100 to 500 ° C.) of 9.5 to 11.0 * 10 -6 K -1 .
  • the coefficient of thermal expansion is set to a desired value in particular through the type and quantity of the crystal phases present in the glass ceramic and the chemical composition of the glass ceramic.
  • the brightness L according to EN ISO 11664-4 of the lithium silicate glass ceramic is preferably more than 70, in particular more than 80 and particularly preferably more than 85.
  • the lithium silicate glass ceramic has a translucency, measured as a contrast value (CR) according to British Standard BS 5612, of preferably more than 60, in particular more than 65 and particularly preferably more than 75.
  • CR contrast value
  • the lithium silicate glass ceramic according to the invention therefore offers a desirable combination of advantageous optical properties and mechanical properties, such as are sought in particular for a dental material.
  • corresponding composition means that these precursors contain the same components in the same amounts as the lithium silicate glass-ceramic, the components, with the exception of fluorine, being calculated as oxides, as is customary for glasses and glass-ceramics.
  • a starting glass which contains the components of the lithium silicate glass ceramic according to the invention.
  • the starting glass therefore contains in particular suitable amounts of SiO 2 , Li 2 O and WO 3 and / or MoO 3 , which are required to form the glass ceramic according to the invention with lithium silicate as the main crystal phase and scheelite and / or powellite as the further crystal phase.
  • the starting glass can also contain other components, in particular CaO and / or SrO, as specified above for the lithium silicate glass ceramic according to the invention. All those embodiments are preferred for the components of the starting glass which are also specified as preferred for the components of the lithium silicate glass ceramic according to the invention.
  • a starting glass of this type which contains seeds for the crystallization of lithium metasilicate, lithium disilicate, scheelite and / or powellite.
  • the invention also relates to a starting glass which contains 0 to 6.0% by weight CaO and 8.0 to 20.0% by weight Li 2 O and optionally further components of the lithium silicate glass ceramic according to the invention and seeds for the crystallization of Scheelite in the form of Ca-Scheelite (CaWO 4 ) and / or Sr-Scheelite (SrWO 4 ) and / or for the crystallization of Powellite in the form of Ca-Powellite (CaMoO 4 ) and / or Sr-Powellite (SrMoO 4 ) contains .
  • the further preliminary stage starting glass with nuclei By heat treatment of the starting glass, the further preliminary stage starting glass with nuclei can first be produced.
  • the lithium silicate glass ceramic according to the invention can then be produced by heat treatment of this further preliminary stage. It is preferred to form the lithium silicate glass ceramic according to the invention by heat treatment of the starting glass with nuclei.
  • the starting glass prefferably to subject the starting glass to a heat treatment at a temperature of 440 to 550 ° C., in particular 460 to 530 ° C., for a period of preferably 5 to 60 minutes, in particular 10 to 30 minutes, in order to germinate the starting glass for to produce the crystallization of lithium metasilicate, lithium disilicate, scheelite and / or powellite.
  • the starting glass with nuclei is further preferred to subject the starting glass with nuclei to a heat treatment at a temperature of 550 to 940 ° C., in particular 580 to 920 ° C. for a period of 5 to 90 minutes, preferably 10 to 60 minutes, in order to form the lithium silicate glass ceramic to manufacture.
  • the invention also relates to a method for producing the lithium silicate glass ceramic according to the invention, in which the starting glass with the components of the lithium silicate glass ceramic or the starting glass with seeds with the components of the lithium silicate glass ceramic has at least one heat treatment in the range from 550 to 940 ° C for a Duration of in particular 5 to 90 minutes, preferably 10 to 60 minutes and particularly preferably 10 to 30 minutes.
  • the starting glass and the starting glass with nuclei can be subjected to the at least one heat treatment, for example in the form of a solid glass blank, a powder compact or a powder.
  • the at least one heat treatment carried out in the method according to the invention can also be performed in the context of hot pressing or Sintering of the starting glass or the starting glass with germs takes place.
  • the starting glass is produced in particular in such a way that a mixture of suitable starting materials, such as carbonates, oxides, and phosphates, at temperatures of in particular 1300 to 1700 ° C, preferably 1500 to 1600 ° C, for a duration of 0, 5 to 3 h, preferably 1 to 3 h is melted.
  • suitable starting materials such as carbonates, oxides, and phosphates
  • the glass melt obtained can be poured into water to form glass granules, and the granules obtained can then be melted again.
  • the melt can then be poured into molds in order to produce blanks of the starting glass, so-called solid glass blanks or monolithic blanks.
  • the cooling is preferably carried out from a temperature of 440 to 550 ° C. at a cooling rate of 2 to 3 K / min down to room temperature. This is particularly advantageous for producing stress-free glass products.
  • the starting glass can also be processed into a powder.
  • the starting glass is then subjected to at least one heat treatment, e.g. in the form of a solid glass blank, a powder compact or in the form of a powder. It is preferred that a first heat treatment is carried out first in order to produce a starting glass with nuclei which are suitable for the formation of lithium metasilicate, lithium disilicate, scheelite and / or powellite crystals.
  • the glass with nuclei is then usually subjected to at least one further thermal treatment at a higher temperature in order to bring about crystallization of lithium silicate, in particular lithium disilicate, and scheelite and / or powellite.
  • the lithium silicate glass-ceramics according to the invention and the glasses described above are in particular in the form of powders, granulates or blanks in any shape and size, e.g. monolithic blanks such as platelets, cuboids or cylinders, or powder compacts, in unsintered, partially sintered or densely sintered form. They can easily be further processed in these forms. However, they can also be in the form of dental restorations such as inlays, onlays, crowns, veneers, shells or abutments.
  • Dental restorations such as bridges, inlays, onlays, crowns, veneers, shells or abutments can be produced from the glass ceramics according to the invention and the glasses described above.
  • the invention therefore also relates to their use for the production of dental restorations. It is preferred that the glass ceramic or the glass by pressing or machining is given to give the shape of the desired dental restoration.
  • the pressing is usually carried out under increased pressure and temperature. It is preferred that the pressing takes place at a temperature of 700 to 1200 ° C. It is also preferred to carry out the pressing at a pressure of 2 to 10 bar.
  • the desired change in shape is achieved through the viscous flow of the material used.
  • the starting glass described above and in particular the starting glass with nuclei described above and the lithium silicate glass ceramic according to the invention can be used for the pressing.
  • the glasses and glass ceramics can be used in particular in the form of blanks of any shape and size, e.g. solid blanks or powder compacts, e.g. in unsintered, partially sintered or densely sintered form.
  • the machining is usually carried out by material-removing processes and in particular by milling and / or grinding. It is particularly preferred that the machine processing is carried out as part of a computer-aided method, in particular a CAD / CAM method.
  • the starting glass described above, the starting glass with nuclei described above and the lithium silicate glass ceramic according to the invention can be used for the machining.
  • the glasses and glass ceramics can be used in particular in the form of blanks, e.g. solid blanks or powder compacts, e.g. in unsintered, partially sintered or densely sintered form.
  • the lithium silicate glass ceramic according to the invention is preferably used for machining.
  • this can also be heat-treated in order to reduce the porosity, for example of a porous powder compact used.
  • the glass ceramics according to the invention and the glasses described above are, however, also suitable as coating material for, for example, ceramics and glass ceramics.
  • the invention is therefore likewise directed to the use of the glasses or the glass ceramics according to the invention for coating, in particular, ceramics and glass ceramics.
  • the invention also relates to a method for coating ceramics and glass ceramics, in which glass ceramics or glasses according to the invention are applied to the ceramic or glass ceramic and are exposed to increased temperature.
  • the glass ceramic or the glass is applied in the usual way, for example as a powder, to the material to be coated, such as ceramic or glass ceramic, and then sintered at an elevated temperature.
  • glass ceramic or glass according to the invention for example in the form of pressed powder or monolithic blanks, is pressed on at an elevated temperature, for example 700 to 1200 ° C., and using pressure, for example 2 to 10 bar.
  • the EP 231 773 described method and the press furnace disclosed there are used.
  • a suitable furnace is, for example, the Programat EP 5000 from Ivoclar Vivadent AG, Liechtenstein.
  • the glass ceramic according to the invention with lithium disilicate as the main crystal phase and scheelite and / or powellite as the further crystal phase is present after the coating process has been completed, since such a glass ceramic has particularly good properties.
  • the invention therefore also relates to the use of the glass ceramic according to the invention or the glasses according to the invention as dental material and in particular for producing dental restorations such as crowns, bridges and abutments.
  • a total of 34 glass ceramics according to the invention with the composition given in Table I were produced by melting corresponding starting glasses and subsequent heat treatment for controlled nucleation and crystallization.
  • the starting glasses were melted in a platinum crucible at a temperature T s of 1500 to 1600 ° C. for a period t s of 1 to 2 h and then cooled. This step was repeated for some glasses in order to achieve a higher degree of homogenization.
  • the melt could then be poured in the form of blocks, for example, or used to produce glass frits, for example.
  • the solidified glasses were transferred to a muffle furnace which was preheated to temperatures T Kb of 460 to 530 ° C., held at this temperature for a period t Kb of 10 to 30 minutes and then cooled without tension.
  • the surfaces of the disks were ground using a 125 ⁇ m diamond disk and the crystal phases were identified by means of X-ray diffraction analyzes (XRD).
  • XRD X-ray diffraction analyzes
  • Example 18 a powder compact was made.
  • the glass frit obtained from the starting glass was dried and ground to an average grain size of ⁇ 90 ⁇ m, based on the number of particles, using an RM200 vibrating mill from Retsch GmbH, Haan, Germany.
  • the ground glass powder was then pressed uniaxially to form small cylinders and these were nucleated, crystallized and sintered in a Programat furnace (Ivoclar Vivadent AG) in two stages at temperature T Kb for duration t Kb and at temperature T C for duration t C .
  • X-ray diffraction analyzes were carried out on the test specimens produced in this way after grinding the surfaces with a 125 ⁇ m diamond disc to determine the crystal phases present.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Dispersion Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Molecular Biology (AREA)
  • Plastic & Reconstructive Surgery (AREA)
  • Epidemiology (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Glass Compositions (AREA)

Claims (20)

  1. Vitrocéramique à base de silicate de lithium, qui contient 0 à 6,0 % en poids de CaO et contient du silicate de lithium en tant que phase cristalline principale et de la scheelite sous forme de scheelite de Ca (CaWO4) et/ou scheelite de Sr (SrWO4) et/ou de la powellite sous forme de powellite de Ca (CaMoO4) et/ou powellite de Sr (SrMoO4) en tant qu'autres phases cristallines.
  2. Vitrocéramique selon la revendication 1, qui contient 8,0 à 20,0, en particulier 11,0 à 17,0 et de préférence 13,0 à 15,0 % en poids de Li2O.
  3. Vitrocéramique selon la revendication 1 ou 2, qui contient 51,0 à 77,0, en particulier 55,0 à 75,0 et de préférence 64,0 à 74,0 % en poids de SiO2.
  4. Vitrocéramique selon l'une quelconque des revendications 1 à 3, dans laquelle la quantité combinée de CaO et SrO vaut en particulier 0,1 à 10,0, de préférence 0,5 à 7,0 et de façon particulièrement préférée 1,0 à 5,0 % en poids.
  5. Vitrocéramique selon l'une quelconque des revendications 1 à 4, qui contient 0,1 à 4,0 et de préférence 0,5 à 2,0 % en poids de CaO.
  6. Vitrocéramique selon l'une quelconque des revendications 1 à 5, qui contient 0 à 10,0, en particulier 0,1 à 7,0 et de préférence 0,5 à 4,0 % en poids de SrO.
  7. Vitrocéramique selon l'une quelconque des revendications 1 à 6, qui contient 0 à 12,0, en particulier 1,0 à 8,0 et de préférence 3,0 à 5,0 % en poids de MoO3.
  8. Vitrocéramique selon l'une quelconque des revendications 1 à 7, qui contient 0 à 22,0, en particulier 1,0 à 14,0 et de préférence 4,0 à 7,0 % en poids de WO3.
  9. Vitrocéramique selon l'une quelconque des revendications 1 à 8, qui contient 1,5 à 6,0, en particulier 2,0 à 5,0 et de préférence 2,5 à 4,5 % en poids de P2O5.
  10. Vitrocéramique selon l'une quelconque des revendications 1 à 9, qui contient au moins un et de préférence la totalité des composants suivants en les quantités indiquées : Composant % en poids SiO2 51,0 - 77,0 Li2O 8,0 - 20,0 SrO 0 - 10,0 MoO3 0 - 12,0 WO3 0 - 22,0 MeI 2O 0 - 6,0 MeIIO 0 - 4,0 MIII 2O3 0 - 11,0 MeIVO2 0 - 11,0 P2O5 1,5 - 6,0 MeV 2O5 0 - 11,5 F 0 - 2,0,
    MeI 2O désignant un oxyde de métal alcalin à l'exception de Li1O,
    MeIIO désignant un oxyde d'élément divalent à l'exception de CaO et SrO,
    MeIII 2O3 désignant un oxyde d'élément trivalent,
    MeIVO2 désignant un oxyde d'élément tétravalent à l'exception de SiO2 et
    MeV 2O5 désignant un oxyde d'élément pentavalent à l'exception de P2O5.
  11. Vitrocéramique selon l'une quelconque des revendications 1 à 10, qui contient du silicate de lithium sous forme de disilicate de lithium et/ou métasilicate de lithium.
  12. Vitrocéramique selon l'une quelconque des revendications 1 à 11, qui contient de la scheelite sous forme de scheelite de Ca (CaWO4) et/ou scheelite de Sr (SrWO4).
  13. Vitrocéramique selon l'une quelconque des revendications 1 à 12, qui contient de la powellite sous forme de powellite de Ca (CaMoO4) et/ou powellite de Sr (SrMoO4).
  14. Vitrocéramique selon l'une quelconque des revendications 1 à 13, qui entre en fluorescence sous excitation par de la lumière de longueur d'onde 254 nm.
  15. Vitrocéramique selon l'une quelconque des revendications 1 à 14, qui présente une opacité aux rayons X selon EN ISO 4049 de plus de 120 %, en particulier plus de 150 % et de préférence plus de 180 %.
  16. Vitrocéramique selon l'une quelconque des revendications 1 à 15, qui présente une résistance à la rupture biaxiale selon ISO 6872 (2015) (essai au piston sur trois billes) de plus de 300, en particulier plus de 350 et de préférence plus de 400 MPa.
  17. Verre de départ, qui contient les composants de la vitrocéramique selon l'une quelconque des revendications 2 à 10 et contient des germes pour la cristallisation de scheelite sous forme de scheelite de Ca (CaWO4) et/ou scheelite de Sr (SrWO4) et/ou pour la cristallisation de powellite sous forme de powellite de Ca (CaMoO4) et/ou powellite de Sr (SrMoO4).
  18. Procédé pour la production de la vitrocéramique selon l'une quelconque des revendications 1 à 16, dans lequel on soumet un verre de départ, qui contient les composants de la vitrocéramique, en particulier le verre de départ comportant des germes selon la revendication 17, à au moins un traitement thermique dans la plage de 550 à 940 °C.
  19. Procédé selon la revendication 18, dans lequel
    (a) on soumet le verre de départ à un traitement thermique à une température de 460 à 530 °C pendant une durée de 10 à 30 min, afin de former le verre de départ comportant des germes, et
    (b) on soumet le verre de départ comportant des germes à au moins un traitement thermique à une température de 580 à 920 °C pendant une durée de 10 à 60 min, afin de former la vitrocéramique à base de silicate de lithium.
  20. Utilisation de la vitrocéramique selon l'une quelconque des revendications 1 à 16 ou du verre de départ comportant des germes selon la revendication 17 en tant que matériau dentaire, en particulier pour la fabrication de restaurations dentaires.
EP17174068.1A 2017-06-01 2017-06-01 Vitrocéramique à base de silicate de lithium ayant une phase cristalline powellite ou scheelite Active EP3409648B1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
ES17174068T ES2862162T3 (es) 2017-06-01 2017-06-01 Vitrocerámica de silicato de litio con fase cristalina de scheelita o powellita
EP17174068.1A EP3409648B1 (fr) 2017-06-01 2017-06-01 Vitrocéramique à base de silicate de lithium ayant une phase cristalline powellite ou scheelite
US15/989,856 US10626045B2 (en) 2017-06-01 2018-05-25 Lithium silicate glass ceramic with scheelite or powellite crystal phase

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP17174068.1A EP3409648B1 (fr) 2017-06-01 2017-06-01 Vitrocéramique à base de silicate de lithium ayant une phase cristalline powellite ou scheelite

Publications (2)

Publication Number Publication Date
EP3409648A1 EP3409648A1 (fr) 2018-12-05
EP3409648B1 true EP3409648B1 (fr) 2021-01-06

Family

ID=58992710

Family Applications (1)

Application Number Title Priority Date Filing Date
EP17174068.1A Active EP3409648B1 (fr) 2017-06-01 2017-06-01 Vitrocéramique à base de silicate de lithium ayant une phase cristalline powellite ou scheelite

Country Status (3)

Country Link
US (1) US10626045B2 (fr)
EP (1) EP3409648B1 (fr)
ES (1) ES2862162T3 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11414340B2 (en) * 2017-10-02 2022-08-16 Shofu Inc. High strength lithium silicate glass ceramic having high shielding property
CN110357424A (zh) * 2019-06-26 2019-10-22 中国计量大学 一种复相荧光玻璃及其低温高压烧结制备方法
CN113200681B (zh) * 2021-05-21 2022-05-27 西南科技大学 一种固化含钼高放核废的萤石基玻璃陶瓷基材的制备方法
CN114605075A (zh) * 2022-03-30 2022-06-10 山东国瓷功能材料股份有限公司 一种含钨酸镉晶相的荧光玻璃陶瓷
CN114790082A (zh) * 2022-03-30 2022-07-26 山东国瓷功能材料股份有限公司 一种含钨酸锌晶相的荧光玻璃陶瓷

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2451121A1 (de) 1973-10-31 1975-05-07 Gen Electric Verfahren zum herstellen von glaskeramiken
CH668699A5 (de) 1986-01-17 1989-01-31 Sonja Wohlwend Erne Verfahren zum herstellen von zahnersatzteilen.
US6420288B2 (en) * 1997-11-10 2002-07-16 Ivoclar Ag Process for the preparation of shaped translucent lithium disilicate glass ceramic products
ES2581452T3 (es) 2010-04-16 2016-09-05 Ivoclar Vivadent Ag Vitrocerámica y vidrio de silicato de litio con óxido de metal de transición
KR20140077949A (ko) 2011-10-14 2014-06-24 이보클라 비바덴트 아게 6가 금속 산화물을 포함하는 리튬 실리케이트 유리 세라믹 및 리튬 실리케이트 유리
US10377661B2 (en) * 2014-05-16 2019-08-13 Ivoclar Vivadent Ag Glass ceramic with SiO2 as the main crystalline phase
EP3150563B1 (fr) * 2015-09-30 2019-05-22 Ivoclar Vivadent AG Vitroceramique en silicate de lithium-wollastonite

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
US10626045B2 (en) 2020-04-21
ES2862162T3 (es) 2021-10-07
US20190047905A1 (en) 2019-02-14
EP3409648A1 (fr) 2018-12-05

Similar Documents

Publication Publication Date Title
EP2765977B1 (fr) Vitrocéramique et verre en silicate de lithium, ayant un oxyde métallique monovalent
EP2765974B1 (fr) Vitrocéramique et verre en silicate de lithium, ayant un oxyde métallique divalent
EP2765975B1 (fr) Vitrocéramique et verre en silicate de lithium, ayant un oxyde métallique trivalent
EP2792345B1 (fr) Vitrocéramique et verre au lithium-silice ayant une teneur en oxyde de césium
DE10336913B4 (de) Verwendung eines Lithiumsilicatmaterials
EP2844213B1 (fr) Vitrocéramique à l'apatite et au lithium-silice
EP3409648B1 (fr) Vitrocéramique à base de silicate de lithium ayant une phase cristalline powellite ou scheelite
EP2765976B1 (fr) Vitrocéramique et verre en silicate de lithium, ayant un oxyde métallique tétravalent
EP3135641A1 (fr) Vitrocéramique en alpha quartz et silicate de lithium
EP3152172B1 (fr) Utilisation d'une vitrocéramique avec du quartz alpha comme phase cristalline principale comme matériau dentaire
EP2765979B1 (fr) Vitrocéramique et verre en silicate de lithium, ayant un oxyde métallique pentavalent
EP3050856B1 (fr) Vitrocéramique en diopside-lithium-silice
EP2868634A1 (fr) Vitrocéramique à l'apatite et au lithium-silice avec oxyde de métal de transition
EP2765978B1 (fr) Vitrocéramique et verre en silicate de lithium, ayant un oxyde métallique hexavalent
DE202011110343U1 (de) Lithiumsilikat-Glaskeramik und -Glas mit Gehalt an ZrO2
EP3696149A1 (fr) Vitrocéramique fluorescente et verres contenant du cérium et de l'étain
EP2930156A1 (fr) Vitrocéramique avec phase cristalline de mélange de quartz
EP3150563A1 (fr) Vitroceramique en silicate de lithium-wollastonite
EP4201901A2 (fr) Vitrocéramique à base de silicate de lithium et contenant du cuivre
WO2022179935A1 (fr) Vitrocéramique comprenant des phases cristallines à mélange de quartz
EP4201900A2 (fr) Vitrocéramique à base de silicate de lithium et contenant de l'étain
EP4140963A1 (fr) Vitrocéramique au silicate de lithium facile à usiner
EP4140962A1 (fr) Vitrocéramique au silicate de lithium facile à usiner

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN PUBLISHED

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20190605

RBV Designated contracting states (corrected)

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

INTG Intention to grant announced

Effective date: 20201112

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1352182

Country of ref document: AT

Kind code of ref document: T

Effective date: 20210115

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 502017008917

Country of ref document: DE

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REG Reference to a national code

Ref country code: CH

Ref legal event code: NV

Representative=s name: KELLER SCHNEIDER PATENT- UND MARKENANWAELTE AG, CH

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20210106

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG9D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210506

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210406

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210106

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210106

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210407

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210406

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210106

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210106

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210106

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210106

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210106

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210506

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 502017008917

Country of ref document: DE

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2862162

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20211007

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210106

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210106

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210106

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210106

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210106

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210106

26N No opposition filed

Effective date: 20211007

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210106

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210106

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210106

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20210630

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210601

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210601

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210506

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210630

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210206

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210106

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230607

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20170601

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20230426

Year of fee payment: 7

Ref country code: FR

Payment date: 20230508

Year of fee payment: 7

Ref country code: DE

Payment date: 20230522

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 20230509

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20230508

Year of fee payment: 7

Ref country code: ES

Payment date: 20230704

Year of fee payment: 7

Ref country code: CH

Payment date: 20230702

Year of fee payment: 7

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210106